Standardization methods Calibration

Provided that the balance is functioning correctly, the main source of error is in the weights themselves these should be calibrated by one of the standard methods so that their relative values are known, and they should be carefully cleaned with tissue paper and checked from time to time. To make the best use of the balance, weighing should be carried out by the method of swings, but for this purpose it is necessary first to determine the sensitivity of the balance. 

Examine a procedure from Standard Methods for the Analysis of Waters and Wastewaters (or another manual of standard analytical methods), and identify the steps taken to compensate for interferences, to calibrate equipment and instruments, to standardize the method, and to acquire a representative sample. 

Since a standard additions calibration curve is constructed in the sample, it cannot be extended to the analysis of another sample. Each sample, therefore, requires its own standard additions calibration curve. This is a serious drawback to the routine application of the method of standard additions, particularly in laboratories that must handle many samples or that require a quick turnaround time. For example, suppose you need to analyze ten samples using a three-point calibration curve. For a normal calibration curve using external standards, only 13 solutions need to be analyzed (3 standards and 10 samples). Using the method of standard additions, however, requires the analysis of 30 solutions, since each of the 10 samples must be analyzed three times (once before spiking and two times after adding successive spikes). 

The method of standard additions can be used to check the validity of an external standardization when matrix matching is not feasible. To do this, a normal calibration curve of Sjtand versus Cs is constructed, and the value of k is determined from its slope. A standard additions calibration curve is then constructed using equation 5.6, plotting the data as shown in Figure 5.7(b). The slope of this standard additions calibration curve gives an independent determination of k. If the two values of k are identical, then any difference between the sample s matrix and that of the external standards can be ignored. When the values of k are different, a proportional determinate error is introduced if the normal calibration curve is used. 

Quantitative Analysis for a Single Analyte The concentration of a single analyte is determined by measuring the absorbance of the sample and applying Beer s law (equation 10.5) using any of the standardization methods described in Chapter 5. The most common methods are the normal calibration curve and the method of standard additions. Single-point standardizations also can be used, provided that the validity of Beer s law has been demonstrated. 

Quantitative mass spectrometry, also used for pharmaceutical appHcations, involves the use of isotopicaHy labeled internal standards for method calibration and the calculation of percent recoveries (9). Maximum sensitivity is obtained when the mass spectrometer is set to monitor only a few ions, which are characteristic of the target compounds to be quantified, a procedure known as the selected ion monitoring mode (sim). When chlorinated species are to be detected, then two ions from the isotopic envelope can be monitored, and confirmation of the target compound can be based not only on the gc retention time and the mass, but on the ratio of the two ion abundances being close to the theoretically expected value. The spectrometer cycles through the ions in the shortest possible time. This avoids compromising the chromatographic resolution of the gc, because even after extraction the sample contains many compounds in addition to the analyte. To increase sensitivity, some methods use sample concentration techniques. 

Because of the complex nature of the discharge conditions, GD-OES is a comparative analytical method and standard reference materials must be used to establish a unique relationship between the measured line intensities and the elemental concentration. In quantitative bulk analysis, which has been developed to very high standards, calibration is performed with a set of calibration samples of composition similar to the unknown samples. Normally, a major element is used as reference and the internal standard method is applied. This approach is not generally applicable in depth-profile analysis, because the different layers encountered in a depth profile of ten comprise widely different types of material which means that a common reference element is not available. 

Normally a calibration curve—molar mass against the total retention volume—exists for every GPC column or column combination. As a measure of the separation efficiency of a given column (set) the difference in the retention of two molar masses can be determined from this calibration curve. The same eluent and the same type of calibration standards have to be used for the comparison of different columns or sets. However, this volume difference is not in itself sufficient. In a first approximation the cross section area does not contribute to the separation. Dividing the retention difference by the cross section area normalizes the retention volume for different diameters of columns. The ISO standard method (3) contains such an equation... 

Determinarion of MW and MWD by SEC using commercial narrow molecular weight distribution polystyrene as calibration standards is an ASTM-D5296 standard method for polystyrene (11). However, no data on precision are included in the 1997 edition of the ASTM method. In the ASTM-D3536 method for gel-permeation chromatography from seven replicates, the M of a polystyrene is 263,000 30,000 (11.4%) for a single determination within the 95% confidence level (12). A relative standard deviation of 3.9% was reported for a cooperative determination of of polystyrene by SEC (7). In another cooperative study, a 11.3% relative standard deviation in M, of polystyrene by GPC was reported (13). 

Load Testing Apparatus. The load apparatus used to simulate the working load on the test unit shall be calibrated in accordance with ASTM E-4 Standard Methods of Verification of Testing Machines, so as to assure that the prescribed test load is obtained. 

O Kane, D. J., and Lee, J. (2000). Absolute calibration of luminometers with low-level light standards. Method. Enzymol. 305 87-96. 

External standard method (linear calibration curve of peak areas)... 

Solutions with low content of alcohol and alcohol ether sulfates cannot be analyzed by the two-phase method and specialized procedures have been developed. ISO method 7875/1 [267] is the standard method for analyzing sulfates and other anionic surfactants at very low concentrations, such as in waste-waters. The absorbance of the chloroform layer containing the surfactant-dye complex is spectrometrically measured at 650 nm and quantified using a calibration curve. Different improvements of this method have been developed [268,269]. 

In a multi-year, multi-laboratory situation it is unlikely that the amount of primary standard (PS) will suffice to cover all requests. The next best thing is to calibrate a larger amount of lower-quality secondary standard (SS) against the PS, and to repeat the calibration at specified intervals until both the PS and the SS have been consumed. In this way, consistency can be upheld until a new lot of PS has been prepared and cross-validated against the previous one. In practice, a working standard will be locally calibrated against the SS and be used for the daily method calibration runs. (See Section 4.32.)... 

HPA catalyzed liquid phase nitration was eairied out in a Teflon-lined stainless autoclave of 200 mL equipped with a magnetic stirrer. Reactants and HPA were quantitatively added to the autoclave, which was sealed and heated in an oil-bath. Products were analyzed by GC with OV-101 30 m capillary column and FID detector by using calibrated area normalization and internal standard method. All products were confirmed by GC-MASS analysis. 

One possibility is that although averages for polystyrene standards require correction, those for PMMA would not According to symmetrical axial dispersion theory (5) the correction depends upon both the slope of the calibration curve (different for each polymer type) and the variance of the chromatogram of a truly monodisperse sample. Furthermore, the calibration curve to be utilized can be obtained from a broad standard as well as from monodisperse samples. The broad standard method may itself incorporate some axial dispersion correction depending upon how the standard was characterized. 

Figure 3. Molecular weight calibration curves for polyvinyl chloride obtained using universal calibration and one and two broad MWD standards (two broad standard method (0) [rj = 7.06 X 10 single broad standard method ...

Detection RI 16X, SP4050 Attenuation 10 Chart speed - Icm/min Analysis time - 24 min Total plate count - 2(10 ) plates Polydichlorophosphazene and cyclic trimer and tetran r standards were used for calibration. Standard methods were applied for integrating peak areas. 

Guillemin, C. L., Calibrating chromatographs on-line. Deferred standard method, Instrum. Technol., 22(4), 43, 1975. 

The determination of the relationship between detector response and the sample concentration is termed the calibration of the method. There are two types of methods in use for the quantitative analysis of a sample, i.e., the external standard and the internal standard method. An external standard method is a direct comparison of the detector response of a pure compound (standard) to a sample.2 The calibration of the method is performed by preparing standards of varying concentration and analyzing them by a developed method. Method 1 (below) was developed for toluene, and standards of varying concentration were prepared and analyzed. The results obtained are summarized in Table 2 see Figure 3. 

Table 2 Calibration Data for External Standard Method...

Figure 4 Calibration of external and internal standard method. Chromatographic conditions — column 30 cm x 3.9 mm p-Bondapak C18 (10-pm particle size) mobile phase water acetonitrile (50 50) flow rate 1.5 ml/min column temperature ambient detector wavelength 254 nm. (A) External standard method, (B) internal standard method.

Calibration of an internal standard method is done by preparing standard samples of varying concentration. The same amount of IS is added to each, and the standard samples are analyzed using a developed method. The detector response, area or height, of each standard is determined, and a ratio is calculated. The graph of concentration vs. area ratio is plotted. The method is considered linear if the correlation coefficient is 0.99 or better. The response factor RF is calculated as... 

For the example of toluene given above, the external standard method can be converted into an internal standard method by adding anisole (an appropriate internal standard) to both standard and sample. The retention time of anisole is 4.5 minutes if analyzed by the method above. To calibrate the internal standard method for toluene, toluene standards of concentration 0.3 to 1.5 mg/ml containing 0.5 mg/ml anisole were prepared. The detector response as a function of the amount of sample injected is shown in Figure 4B. 

Spark sources are especially important for metal analysis. To date, medium-voltage sparks (0.5-1 kV) often at high frequencies (1 kHz and more), are used under an argon atmosphere. Spark analyses can be performed in less than 30 s. For accurate analyses, extensive sets of calibration samples must be used, and mathematical procedures may be helpful so as to perform corrections for matrix interferences. In arc and spark emission spectrometry, the spectral lines used are situated in the UV (180-380nm), VIS (380-550nm) and VUV (<180 nm) regions. Atomic emission spectrometry with spark excitation is a standard method for production and product control in the metal industry. 

Application to solid polymer/additive formulations is restricted, for obvious reasons. SS-ETV-ICP-MS (cup-in-tube) has been used for the simultaneous determination of four elements (Co, Mn, P and Ti) with very different furnace characteristics in mg-size PET samples [413]. The results were compared to ICP-AES (after sample dissolution) and XRF. Table 8.66 shows the very good agreement between the various analytical approaches. The advantage of directly introducing the solid sample in an ETV device is also clearly shown by the fact that the detection limit is even better than that reported for ICP-HRMS. The technique also enables speciation of Sb in PET, and the determination of various sulfur species in aramide fibres. ETV offers some advantages over the well-established specific sulfur analysers very low sample consumption the possibility of using an aqueous standard for calibration and the flexibility to carry out the determination of other analytes. The method cannot be considered as very economic. 

The main advantages of CPAA as a surface characterisation method are that it requires no sample preparation, its high accuracy and its low detection limits. It is an independent method, because no standard samples calibrated by other methods are needed, so that its value may lie in its ability to calibrate standard samples for other, more routine analytical methods. 

Sieve analysis, based on either vibratory or suction principle, uses a series of standard sieves calibrated by the National Bureau of Standards. The method is generally used for screening coarse particles down to a material as fine as 44 pm (No. 325 sieve). Sieves produced by photoetching and electroforming techniques are now available with apertures from 90 down to 5 pm. 

Koda S, Kimura T, Kondo T, Mitome H (2003) A standard method to calibrate sonochemical efficiency of an individual reaction system. Ultrason Sonochem 10 149-156... 

---